Synthesis and photoluminescence characterizations of Zn2+ and Tb3+ codoped CeO2 phosphors for temperature sensing applications

Cyan light-emitting Ce_0.985-xZn_xO₂:0.015 Tb³⁺ (x = 0 to 0.2) phosphors were synthesized using the ethylenediaminetetraacetic acid-assisted hydrothermal method. The X-ray diffraction and refinement analyses of the prepared phosphors indicated that the formed face-centered cubic structure remained intact even after the doping of large quantities of Zn²⁺ ions. However, the incorporation of Zn²⁺ ions increased the Ce³⁺/Ce⁴⁺ ratio, resulting in the enhancement of oxygen vacancies in the prepared phosphors. The generation of oxygen vacancies caused the evolution of a broad photoluminescence emission band ranging from 400 to 525 nm with a characteristic Tb³⁺ emission of approximately 543 nm. Two-emission regions in Ce_0.885Zn_0.1O₂:0.015 Tb³⁺ phosphors were utilized for measuring the fluorescence intensity ratio (FIR) as a function of temperature ranging from 303 to 523 K. At 523 K, the FIR values dropped to approximately 40% of the starting temperature value. The variation of FIR values followed the Boltzmann behavior. The Boltzmann fitting demonstrated the feasibility of the present phosphors for temperature sensor applications. The optimum absolute sensor sensitivity of Ce_0.885Zn_0.1O₂:0.015 Tb³⁺ phosphors was measured to be 0.0043 K⁻¹ at 398 K with a resolution of approximately 1 K⁻¹. Moderate temperature sensitivity, negligible hysteresis loop, and excellent reversibility revealed the suitability of Ce_0.885Zn_0.1O₂:0.015 Tb³⁺ phosphors for sensing the temperature in various electronic devices.     

Macro-/mesoporous Metal–Organic Frameworks Templated by Amphiphilic Block Copolymers Enable Enhanced Uptake of Large Molecules

The first synthesis of hierarchical porous metal–organic frameworks (HP-MOFs) is reported through a solvent evaporation-induced co-assembly of polystyrene-block-poly(ethylene oxide) (PS-b-PEO) and MOF building blocks. The growth of MOFs is restricted to confined spaces formed by self-assembled PS-b-PEO, and mesopores and/or macropores are created after removing PS-b-PEO by solvent rinsing. This approach avoids phase separation and competitive interactions between templates and MOF building blocks. Both amorphous and crystalline HP-MOFs can be synthesized by finely controlling MOF growth conditions. Additionally, HP-MOFs (ZIF-L sheets) with honeycomb-like channels show significantly enhanced incorporation of large guest molecules compared to microporous MOFs. This study establishes an efficient synthetic strategy for preparing HP-MOFs with highly accessible mesopores and macropores for applications involving large molecules.     

A Fluorescent Unnatural Mannosamine Derivative with Enhanced Emission Upon Complexation with Cucurbit[7]uril

Metabolic incorporation of unnatural functionality on glycans has allowed chemical biologists to observe and affect cellular processes. Recent work has resulted in glycan-fluorophore structures that allow for direct visualization of glycan-mediated processes, shining light on their role in living systems. This work describes the serendipitous discovery of a small chemical reporter-fluorophore. Investigations into the mechanism of fluorescence arising from (trimethylsilyl)methylglycine appended on mannosamine suggest rigidity and restriction of lone pair geometry contribute to the fluorescent behaviour. In fact, in situ cyclization and encapsulation in cucurbit[7]uril enhance fluorescence to levels that can be observed in live cells. While the reported unnatural mannosamine does not traverse the sialic acid biosynthetic pathway, this discovery may lead to small, “turn-on” chemical reporters for incorporation in living systems.     

Incorporation limit of MoO3 in sodium borosilicate glasses

Optimizing the concentration of molybdenum incorporated in a borosilicate glass matrix is essential in the vitrification of high-level radioactive waste. However, the incorporation limit of MoO₃ in fundamental borosilicate systems has been rarely correlated with the local structure of the molybdenum cations. This study investigates the variations in the incorporation limit of MoO₃ in ternary sodium borosilicate glass upon varying the B₂O₃/(SiO₂ + B₂O₃) ratio (i.e., B)_. The incorporation limit of MoO₃ was less than 3 mol% in the low-B region (B < 0.7), where molybdenum cations mainly existed as [MoO₄]²⁻. However, when B was higher than 0.85, the incorporation limit was higher than 6 mol%, and the Raman spectra indicated the presence of octahedrally coordinated molybdenum cations, essential to stabilize the Mo–O–Mo linkage. The variation in the local structure of molybdenum cations can be explained by the available amount of non-framework cations compensating for the negative charge near [MoO₄]²⁻. These results allow the development of glass compositions with a high incorporation limit of MoO₃ simply by controlling the local structure near the molybdenum cations.